Method of treating fibrous materials and product thereof



Patented Nov. 30,1943

UNITED STATES PATENT OFFICE METHOD OF TREATING FIBROUS MATE- x RIALS AND PRODUCT THEREOF Andrew Szegvari, Fairlawn, and Adrian H. Feikert,-Wadsworti1, Ohio, minors to American Anode Inc., Akron, i|io, a corporation of Delaware No Drawing. Application March as, 1940,

Serial No. 325.051 22 Claims. (Cl. 111-47) This invention relates to a method of treating a wide variety of fibrous materials including fibers in unfabricated as well as fabricated form in order to produce -fibrous articles. and products exhibiting to a high degree certain desired properties of long life, wear resistance and resistance to 'a variety of other factors and influences involved in the usual service of the various articles and products. The invention also contemplates the treated fibrous products obtained by practicing the method. More particularly, the invention involves the application to fibrous material of a coating deposit of the solids from an aqueous dispersion of polyisobutylene or similar material preferably in admixture with certain other materials for modifying the characteristics of the polyisobutylene. The invention is'especially concerned with the treatment of fibrous materials with aqueous dispersions of certain tough, elastic and permanently resilient, highmolecular weight polymers of isobutylene and analogous olefins.

There are now available onthemarket in this country under the trade-namefvist'anex" certain permanently resilient paramnic materials prepared by polymerizing olefins of low molecular weight. Similar materials have also b'een sold duce a variety ,of polymers of much higher molecular weights. Apparently depending somewhat upon the particular method of polymerization employed, the polymers may consist praclar weights extendingfrom around 800 hp to the region of average molecular weights of from 25,000 to- :30,000 are liquid or liquid-like in nature. The higher polymers having average molecular weights in the range extending from the region of 25,000 to 30,000 up to 100,000 or 200,000 or even 500,000 are quite diiferent in manyphysical properties and are permanently resilient solids as distinguished from the liquid and liquid-like polymers in the lower range of average molecu-' lar weights. In U. 8. Patent No. 2,138,895 assigned to the manufacturers in this country of Vistanex," the term "plastic" is applied to the lower range of liquid-like polymers while, in contra distinction, the term elastic" is applied to the resilient polymers in the higher range of average molecular weigh s.

The liquid and liquid-like plastic polymers in the lower molecular weight range may be dispersed directly in water by commonly used methods of dispersing (emulsifying) insoluble liquid materials in water. 0n the contrary, it is dimcult to prepare a satisfactory dispersion of the higher molecular weight polymers because of their permanently resilientzand non-plastic nature. However, in certain other patent applications hereinafter identified, we have described methods by which the resilient solid polymers may be dispersed directly in-water to produce excellent coltically entirely of polymerized isobutylene. or

may consist principally ofpolymerized isobutylene in admixture, however, with some other polymerized olefins. It is also understood, that other related olefins and iso-ol'eilns may be polymerized; in a similar manner to produce similar polymers;

loidai dispersions. Reference is here made to the other applications for details of the dispersing procedures but it may be noted that one of the preferred procedures involves the use of a conjunctive material such as a rubber (which is understood to include both natural and synthetic rubbers and rubber-type materials, such as natural crude rubber, rubber in the form of latex or other dispersion, reclaimed rubber, bu-' v tadiene rubbers, neoprene, and the like, as well as analogous gums and resins such as gutta percha and balata ester gum, asphalt, rubber derivatives prepared by treating rubber with .sulionic acids, rubber degradation products obtained by dry distilling rubber and including both the volatile oils and the solid residues so produced, chlorinated diphenyl, chlorinated naphthalene, rosin, poly-ethylene dihalides such as the commercial product A. X.F." and like materials.

. Such conjunctive materials are mixed with the polymer is present, in the dispersed particles in a resilient solid state. We have found that such dispersions of reand flexibility as well as in resistance to water and chemicals. Somewhat similarly the dispersions have been mixed with comminuted leather fibers or cotton or other fibers and formed into treating process has heretofore been suggested or a sheet and dried to make artificial leather surpassing prior products in resistance to water permeation, strength and flexibility.

Textile fabrics of various kinds have been water-proofed and gas-proofed with such dispersions of polyisobutylene. ,Balloon fabric impregnated with such a dispersion and dried exhibits ,exceptional strength and low permeability to gases. Leather goods in general. and conveyor and transmission belts of both leather and fabric, are improved by treatment with the dispersions.

-A mass of glass wool in suitable form impregnated with such a dispersion of polyisobutylene provides an efficient filter for air-conditioning systems and especially for filtering corrosive liquids or gases. Woven glass textile tapes impregnated with the dispersions are especially useful for heat-resistant gaskets and as protective coatings for plating racks used in chromium and other plating baths. The dispersions are also valuable for treating clothing to be worn for protectionagainst toxic gases and corrosive chemicals.

Emulsions or dispersions of the liquid-like polymers of isobutylene and also dispersions of the resilient polymers prepared without the use of conjunctive agents are satisfactory to some degree in practically all the foregoing applications, and, in some cases, are equally as satisfactory as the dispersions containing conjunctive materials. Generally, however, the dispersions of resilient solid polymers associated with conjunctive materials are definitely superior for treating fibrous materials and are preferred for most uses in that field.

Aqueous dispersions of polyisobutylene of the character described have thus far found their widest application in the treatment of women's silk and synthetic silk or rayon hosiery for the purpose of improving the life and wear characteristics of the hose. Many treatments for this purpose have been suggested from time to time,

including treatments with rubber, with rubber derivatives, and with a variety of different natural and synthetic resins in many different forms and including an equally wide variety of processes and conditions for applying the treating materials to the hose. Insofar as applicants are aware, however, none of the many prior processes has been used commercially to any substantial extent. The reason is apparent. Silk hose and-the like are quite sheer and flimsy and a satisfactory treatment should strengthen or reenforce the hose and the constituent yarns" sufficiently to provide reasonably long life and, especially, to provide added resistance to snagging and resultant running or laddering of the knitted fabric. At the same time, the treatment must not stiffen the hose to any substantial degree, must not alter the natural silky feel unduly, and must not impart any undesirable odor to the hose nor impair their appearance. These requirements are to some extent seemingly mutually inconsistent and contradictory and no material -01 devised which satisfactorily meets all the requirements. Resins generally tend to stiffen the hose and attempts at plasticization have not been effective in relieving such stiffness. Rubber, while sufiiciently flexible, involves undesirable odors and surface characteristics imparting an undesirable feelto the hose. Other materials which have been proposed present similar undesirable features.

We have found that silk and other sheer hosiery may be treated with aqueous dispersions of the high molecular weight resilient, solid polymers of isobutylene, preferably in association with a conjunctive material of .the character hereinabove described, and that the treated hose exhibit exceptional flexibility, excellent resistance to snagging, tearing, running and laddering, unusually long life, andgood resistance to.

repeated washings. Also, the treated hose are satisfactorily free of objectionable odors and undesirable surface characteristics such as tackiness. It has further been found that especially satisfactory reenforcement and surface characteristics are obtained if the treatin dispersion also contains a tack-destroying material of a resinous nature such as a phenolic resin, shellac, or a copolymer of butadiene and acrylic nitrile such as the commercial product "Perbunan." Such tack-destroying resins preferably are incorporated in the treating dispersion in quantities varying from'5% to 25% by weight.

The exceptionally satisfactory results obtained in treating silk hosiery according to the present invention appear to result in part from the modifying effects of added materials, especially the conjunctive materials and the tack-destroying materials, and in part from proper physical application of the treating material which involves a number of procedural details apparently contributing valuably to the successful end result..

It accordingly appears. that the invention may best be understood by considering a specific, detailed description of a preferred embodiment of the invention. The following detailed description is therefore to be taken as illustrative and not limitative of the invention.

Best results are attained if the hose are treated after they have been "boiled off in the usual manufacturing procedure and before they are dyed, although satisfactory results may be obtained by treating dyed hose provided the dye used is of such nature that the present treatment centrifuging the hose for a few minutes.

' the dye.

will not spot, discolor or otherwise interfere with The boiled off but undyed' hose are first immersed in a bath of introfying solution preferably containing at least one saponaceous material and an alkaline material. An especially satisfactory introfying solution may be prepared by adding to water the following quantities of materials for each gallon of water: 25 c. c. of 20% potassium oleate solution, 20 c. c. of a 15% solution of the commercial product known as ,Im-

mersol TX," 15 c. c. of the synthetic saponaceousshould be noted here that many manufacturers treat boiled off" hose with a neutral soap solution as a part of the regula manufacturing procedure. In treating such hose according to the present invention, the introfying solution treatment may be dispensed with in many cases as the neutral soap treatment has a similar although somewhat less eflicient introfying effect. More uniform results are attained if the introfying treatment is employed. whether or not the hose have been treated with soap or the like.

The prepared hose then are immersed in an aqueous dispersion of solid, resilient polyipobutyl- Otherwise a' non-uniform coating is produced.

i The treated hose'then are mounted onconvenene prepared according to the method of our applications hereinafter identified and preferably containing a conjunctive material and a tackdestroying material as well as other incidental compounding materials. For example, a satisfactory treating disperslon rnay be prepared by admixing 100 parts by weight of Vistanex high molecular weight" (a resilient solid polymer of isobutylene stated to have an\ average molecular weight of around 200,000) and 17 parts of premasticated crude atural rubber as'a conjuncdispersion in emulsion form. The dispersion also should contain vulcanizing agents in sufiicient quantities to vulcanize the rubber conjunctive material present, as well as an age-resistor for the rubber. Such materials may be added according. to well-known rubber dispersion coma pounding practice.

In the illustrative example, the vulcanizing agents may include 2 parts by weight of sulfur, 3.3 parts of organic accelerator of vulcanization, and 2 parts of zinc oxide. 0.4 parts of a commercial age-resistor 'such "as AgeRite White (sym. di beta nephthyl-pphenylene diamine) also should be added. All such compounding materials are added as colloidal dispersions or emulsions according to usual practice. Also, the dispersion may contain added stabilizing agents such as 2.0 parts by weight of phosphotex, a phosphate salt stabilizer. The

treating dispersion may contain from 10% to 50% total solids by weight but preferably con tains in the neighborhood of 20% to total solids. In many instances, it will be desirable to replace the crude rubber conjunctive material of the foregoing example with neoprene or butadiene rubber or similar synthetic rubber or rubbertype material (all within the generic term .a

tive material and dispersing .the mixture 'accord- "ing to the procedure described in our aforementional boarding forms and are dried for 5 minutes at 150 F. to effect coagulation of the distion may be effected by placing the treated hose in a chamber filled'with vapors of a coagulant such as formic acid or acetic acid. The coagulated rubber is then vulcanized by heating for 30 minutes at 220 F. Thereafter, the hose are washed in a 0.5% mild soap solution at-90 F.

rinsed in fresh water, centrifuged-and again dried. The hose are then dyed according to usual practice unless pre-dyed hose have been treated.

The individual yarns and fibers of the treated hose are covered with a coating which is of the order of only 5 micronsin thickness (which is undestood to include variations of from 3 to 10 microns unless otherwise indicated). Notwithstanding the extreme thinness of the coating, the

life and wear characteristics of the hose are improved remarkably and none of the undesirable features of prior treatmentsare presented.

While the detailed procedure hereinabove described has been developed especially for treating silk, rayon, nylon'and other sheer knitted hosiery, substantially the same procedure may be employed advantageously for treating a variety persion on the fibers. If desired, the coagulaof textile and other fabric materials. Thus fab.-

rics and other fibrous structures of wool, cotton.

silk, glass and'synthetic yarns or threads such as nylon and rayon may be treated effectively. by the procedure described,or the treating dis-' persions may be simply spread, brushed, or transferred to the fibrous material by at ansfer roll.

Similarly, many of the features of the hosiery treatment may be applied advantageously to the Jtreatment of the various fibrous materials derubber" as herein employed and as previously indicated) in order to eliminate any trace of natural crude rubber odor and tackiness.

The hose are permitted to remain in the treating dispersion for about 30 seconds after which theyare removed together with a considerable scribed in theearlier paragraphs of this speci cation, All such applications and many variations in details of the procedure and materials described are within the spirit and scope of the invention asdefined by the appended claims.

A part of 1 the subject matter herein disclosed is claimed in 0dr concurrently filed application, Serial No. 325,652, filed March 23, 1940.

This application is a continuation-in-part .of our earlier co-pending applications, Serial No. 308,220, filed December 8, 1939 (now U. S. Patent No. 2,194,958,;granted March 26, 1940); and Serial No; 315,620, filed January 25', 1940, which, in turn, were continuations-in-part of a co-pending application, Serial ltlo. 83,356, filed June 3, 1936.?

phenol-formaldehyde nesin,,removing the hose from the dispersiontogether with a substantial quantity of the dispersion in association hereare passed immediately through tight set rubber covered wringer rolls or otherwise pressed to express a substantial part of the associated dispersion, and the hose are then conveyed between forceful blasts of compressed airor the like to blow bridging films from the interstices of the hose fabric. It is important that the removal of the excess uncoagulated dispersion be effected before any substantial coagulation has occurred.

with in an uncoagulated condition, removing a substantial part of the associated dispersion from the hose by wringing operation, directing a blast of air on the hoseto remove bridging films from the interstices, siibjecting the 1thus treated hose to a/ heat treatment, and thereafter dyeing the ose.

' 2. The method of improving thalife and wear characteristics of sheer hose which comprises treating. the hose with an introi'ying solution, im-

4' A I s am treating the hose with an introiying solution insion together with a substantial quantity of the dispersion in association therewith in an uncoagulated condition, removing a substantial part of the associated. dispersion from the hose by a wringing operation, directing a blast oi air upon the hose to remove bridging films from the-interl5 stices, and subjecting the thus treated hose to a heat treatment.

3. The method of improving the lite and wear ,characteristics of sheer hose which comprises treating the hose with an introiying solution,

removing excess introiyingsolution from the hose, immersing the treated hose in an aqueous dispersion comprising a resilient, solid, high-molecular weight polymer of isobutylene, a plastic material intimately admixed with the isobutylene polymer and a phenol-formaldehyde type resin, removing the hose from the dispersion together with a substantial quantity of the dispersion in association therewith in an uncoagulated condition, removing a substantial part of the associated dispersion from the hose, removing bridging films from the interstices, and subjecting the thus treated hose to a treatment for coagulating the dispersion on the hose.

4. The method of improving the life and wear 5 characteristics of sheer hose which comprises treating the hose with an introiying solution, im-

mersingthe treated hose in an aqueous diapersion comprising a resilient, solid, high-molecular weight polymer of isobutylene and a phenol-iorm- 40 of the associated dispersion from the hose, re-

moving bridging films from the interstices, and subjecting the thus treated hose to a treatment for coagulating the dispersion on the hose.

- 5. The method of improving the life and wear characteristics of sheer hose which comprises I g which comprises associating with the material an treating the hose with an introi'ying solution, immersing the treated hose in an aqueous dispersion comprising a resilient, solid, highemolecular weight polymer of isobutylene and a resinous material, removing the hose from the dispersion together with a substantial quantity of the dispersion in association therewith in an uncoagulated condition, removing a substantial part oi the associated dispersion from the hose, removing the bridging films from the interstices, and subjecting the thus treated hose to a treatment for coagulating the dispersion on the hose.

6. The method of improving the life and wear characteristics of sheer hose which comprises mersing the treated hose in an-aqueous dispersion comprising a resilient solid, high-molecular weight polymer of isobutylene and aresinous tackdestroying material comprising an emulsified of the associated dispersion from the hose, and

subjecting the thus treated hose to a treatment for coagulating the dispersion on the hose.

7. The method 01 improving the lite and wear characteristics of sheer hose which comprises treating the hose with an introiying solution, immersing the treated hose in an aqueous dispersion comprising aresilient, solid, high-molecular weight polymer or isobutylene, removing the hose .irom the dispersion together with a substantial quantity or the dispersionin association therewith in an uncoagulated condition, removing a substantial part or the associated-dispersion from g the hose, andsubjecting the thus treated hose to a treatment for coagulating the dispersion on the hose.

8. The method of improving theme and wear characteristics or sheer hose which comprises treating the hose with an introiying solution, immersing the treated hose in an aqueous dispersion comprising a resilient, solid, high-molecular weight polymerization product having parafiinic characteristics prepared by polymerizing an olefin of low molecular weight, removing the hose.

from the dispersion together with a substantial quantity of the dispersion in association therewith in an uncoagulated condition, removing a substantial part of the associated dispersion from the hose, and subjecting the thus treated hose to 181 treatment for coagulating the dispersion on the ose.

9. The method of treating fibrous material which comprises associating with the material an aqueous dispersion comprising colloidally dispersed solid particles containing a resilient, solid, high molecular weight polymerization product having parafilnic characteristics prepared by polymerizing an olefin of low molecular weight,- the polymerization product being present in the particles in a solid resilient state, and coagulating the dispersion in association with the fibrous material.

10. The method of treating fibrous material which comprises associating with the material an aqueous dispersion comprising a resinous material and colloidally dispersed solid particles containing polyisobutylenein a solid, resilient state, and coagulating the dispersion in association with the fibrous material.

12. The method of treating fibrous material which comprises associating with the material an aqueous dispersion comprising an emulsified phenolic resin together with colloidally dispersed solid particles containing polyisobutylene in a solid, resilient state, and coagulating the dispersion in association with the fibrous material.

13. The method of treating fibrous material which comprises associating with the material an aqueous dispersion comprising a phenol-formal dehyde type resin and polyisobutylene in a solid,

resilient state, and coagulating the dispersion in association with the fibrous material.

14. The method of treating fibrous material which comprises associating with the material an aqueous dispersion comprising a resinous material, a rubber, and polyisobutylene, andcoagulating the dispersion in association with the fibrous material.

15. The method of treating fibrous material which comprises associating with the material an aqueous dispersion comprising colloidally dispersed solid particles containing a resilient, solid high-molecu1ar weight polymer of isobutylene in a solid, resilient state and a material selected from the class consisting of natural rubber and synthetic rubber, and coagulating the dispersion in association with the fibrous material.

16. An article of manufacture comprising fibrous material having associated therewith a deposit of solids comprising resilient, solid highmolecular weight polyisobutylene, a material selected from the class consisting of natural rubber and synthetic rubber intimately admixed with the isobutylene polymer, and a tack-destroying material comprising a phenolic resin.

17. An article of manufacture comprising a sheer textile fabric member and a coating material thereon, said coating material comprising solid, resilient high-molecular weight polyisobutylene, a rubber, and a tack-destroying material comprising a phenolic resin.

18. An article of manufacture comprising a sheer textile fabric member and a coating material thereon, .said coating material comprising solid, resilient high-molecular weight polyisobutylene, a rubber, and a phenol-formaldehyde yp resin.

19. A sheer hose or similar article of wearing apparel having a. coating on the individual yarns thereof, said coating being of the order of five microns in thickness and comprising solid, resilient high-molecular weight polyisobutylene, a rubber and a resinous material.

20. A sheer hose having a coating on the individual yarns thereof, said coating being of the order of five microns in thickness and comprising a resilient, solid, high molecular weight polymer of isobutylene, the coating being substantially free of tackiness.

21. An article of manufacture comprising a sheer textile fabric member and a very thin coating on the individual threads of the fabric, said coating comprising a resilient, solid high-molecular weight polymer of isobutylene, natural rubber, and a phenolic resin, the said coating being substantially odorless and free of tackiness.

22. The method of improving the life and wear characteristics of a sheer textile fabric which comprises immersing the fabric in an aqueous dispersion comprising a resilient, solid, highmolecular weight polymer of isobutylene, natural rubber. and a resinous material; removing the hose from the dispersion together with a substantial quantity of the dispersion in association therewith in an uncoagulated condition; removing a substantial part of the associated dispersion from the hose; and solidifying the dispersion remaining on the hose.

ANDREW SZEGVARI. ADRIAN H. FEIKERT.

CERTIFICATE OF CQRRECTEON. Patent No. 2,555,521. 7 November 50, 19145.

' ANDREW SZEGVARI, ET AL.

It is hereby certified that error appears 'in the above numbered patent requiring correction as follows: In the grant, line 5, name of assignee, for "AMERICAN ANODE IND." read -AMERICAN ANODE mc.--; age 2, first colixmn, line 6, for "5% to 5% read 5% to 50%"; page 5, second column, line 151, for procedure read --procedures--; page 1 first column, line 60, claim 5, for "removing the bridging read --removing bridging--; and

that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 8th day of February, A. D. 191411..

Henry Van Arsdale (Seal) Acting Commissioner of Patents. 

